EP3634921A1 - Procédé de préparation d'une dispersion aqueuse et poudre de dispersion redispersible préparée à partir de celle-ci - Google Patents

Procédé de préparation d'une dispersion aqueuse et poudre de dispersion redispersible préparée à partir de celle-ci

Info

Publication number
EP3634921A1
EP3634921A1 EP18727837.9A EP18727837A EP3634921A1 EP 3634921 A1 EP3634921 A1 EP 3634921A1 EP 18727837 A EP18727837 A EP 18727837A EP 3634921 A1 EP3634921 A1 EP 3634921A1
Authority
EP
European Patent Office
Prior art keywords
acid
group
dispersion
sulfonic acid
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18727837.9A
Other languages
German (de)
English (en)
Inventor
Christian Schmidtke
Ekkehard Jahns
Torben Gaedt
Martin Winklbauer
Klaus Seip
Iris LOESCHER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3634921A1 publication Critical patent/EP3634921A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C04B40/0042—Powdery mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/06—Acrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • C04B2111/00672—Pointing or jointing materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/60—Flooring materials
    • C04B2111/62—Self-levelling compositions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72—Repairing or restoring existing buildings or building materials

Definitions

  • the present invention relates to a process for the preparation of a redispersible dispersion powder, the redispersible dispersion powder obtainable by this process, an aqueous dispersion obtainable after step (1) of this process, and a building material composition containing the redispersible dispersion powder and / or the aqueous dispersion, the use of the redispersible dispersion powder in a building material composition and the use of the aqueous dispersion for the preparation of a redispersible dispersion powder.
  • Aqueous dispersions containing polymer particles are used in building material compositions in order to improve the flexibility, the adhesive properties and / or the flowability of the building material compositions.
  • aqueous dispersions are disadvantageous because the building material compositions are generally required as dry blends. Furthermore, aqueous dispersions are disadvantageous in terms of storage (for example due to frost damage, microorganism attack, etc.) and of transport. In particular, upon prolonged storage originally dispersed uniformly dispersed polymer particles can agglomerate and thus prevent a uniform distribution of the polymer particles in the building material composition. Therefore, dispersion powders are required, which are redispersible and contain polymer particles, in order to improve the flexibility, the adhesion properties and / or the flowability of the building material compositions, as stated above.
  • a particularly expedient method for converting an aqueous dispersion into a redispersible dispersion powder is spray-drying.
  • the aqueous dispersion is sprayed in a stream of hot air and dehydrated.
  • a spray aid is added to the aqueous dispersion.
  • Redispersible dispersion powders therefore usually contain polymer particles and a water-soluble spray aid.
  • emulators may be included.
  • No. 5,922,796 A describes a redispersible dispersion powder comprising a powder of a water-insoluble, film-forming polymer obtainable from at least one ethylenically unsaturated monomer, at least one nonionic emulsifier and at least one water-soluble compound selected from polyelectrolytes which belong to the weak polyacids and contain carboxyl groups as acid groups.
  • No. 6,036,887 A describes redispersible granules comprising at least one active material in the form of a hydrophobic liquid, at least one nonionic emulsifier and at least one water-soluble compound selected from polyelectrolytes which belong to the weak polyacids and contain carboxyl groups as acid groups.
  • WO 03/097721 A1 describes the use of water-soluble polymers consisting of monomers containing monoethylenically unsaturated acid groups in acidic, partially or completely neutralized form and further monomers copolymerized with these monomers as drying agents for the preparation of redispersible powder and / or pulverulent, polymeric dispersant , It is described as preferred that the acid groups of the monomers are at least partially neutralized before, during or after polymerization.
  • WO 97/26295 A1 discloses redispersible polymer powders based on a mixture of water-insoluble polymer and a water-soluble polymeric atomizing protective colloid which contains carboxylic acid groups and is not neutralized or partially neutralized.
  • DE 43 20 220 A1 discloses the use of polymers of acrylamide or acrylic acid ester monomers which carry a sulfonic acid group in the side chain, and further free-radically copolymerizable monomers as auxiliaries in the spray-drying of aqueous dispersions.
  • the spray aids described in the prior art have disadvantages. For example, they are unsuitable for the spray-drying of certain aqueous dispersions or dye the dispersion powder. Above all, there is still room for improvement in the redispersibility of the dispersion powder. In addition, there is a great need to improve the application properties of the redispersible dispersion powder to the effect that the made with the redispersible dispersion powder building material is easy to process, in particular an optimal pot life of about 0.5 h - 2 h.
  • an aqueous dispersion wherein the dispersion contains particles, the particles containing at least one polymer I, wherein the polymer I contains monomer units which are composed of at least one ethylenically unsaturated monomer;
  • step (1) an additive containing a polyoxyalkylene group, preferably a polyoxyethylene group, wherein the degree of ethoxylation is 6 to 50, is present, the additive
  • (A) is admixed as a further component of the mixture from step (1), or (B) is applied in a preceding step by emulsion polymerization on the surface of the particles, or
  • (C) is polymerized in a preceding step as a monomer unit in the polymer I of the particles;
  • step (1) wherein the dispersion resulting from step (1) has a pH of ⁇ 4;
  • step (2) drying the dispersion resulting from step (1) to obtain the redispersible dispersion powder.
  • redispersible dispersion powders can be improved if a polyacid II is used as a spraying assistant and the spray drying is carried out at a pH of ⁇ 4. This is probably due to the acidic pH-enhanced formation of hydrogen bonds between the particles containing the polymer I and the polyacid II. This effect can be enhanced if an additive acting as an emulsifier containing a polyoxyalkylene group is added. It is believed that in this way a protective cover is formed around the particles, which protects the particles during the spray-drying before the filming.
  • the present invention relates to a redispersible dispersion powder obtainable by the process according to the invention.
  • an antiblocking agent is preferably added to the redispersible dispersion powder obtained by the process according to the invention in order to prevent irreversible agglomeration of the polymer particles of the redispersible dispersion powder.
  • the redispersible dispersion powder according to the invention is distinguished by a particularly good redispersibility. This improved property is presumably due to the protective coating of the polyacid and, optionally, the emulsifier around the particles formed by the process according to the invention.
  • the invention further relates to an aqueous dispersion obtainable after step (1) of the process.
  • the dispersion is particularly advantageous for the preparation of the redispersible dispersion powder due to the low pH for the reasons explained above.
  • the invention relates to a building material composition containing
  • the building material composition has improved properties with regard to processability, flexibility, adhesion and possibly flowability.
  • the invention also relates to the use of the inventive redispersible dispersion powder in a building material composition. Furthermore, the invention also relates to the use of the aqueous dispersion according to the invention for producing a redispersible dispersion powder.
  • weight% also called mass fraction
  • Vol% denotes the percentage of the respective component in relation to the sum of all components measured by volume, unless otherwise stated. Furthermore, the sum of all percentages of the specified and unspecified components of a composition is always 100%.
  • the invention relates to a process for the preparation of a redispersible dispersion powder comprising the steps
  • an aqueous dispersion wherein the dispersion contains particles, the particles containing at least one polymer I, wherein the polymer I contains monomer units which are composed of at least one ethylenically unsaturated monomer;
  • step (1) an additive containing a polyoxyalkylene group, preferably a polyoxyethylene group, wherein the degree of ethoxylation is 6 to 50, is present, the additive
  • (A) is admixed as a further component of the mixture from step (1), or
  • (B) is applied in a preceding step by emulsion polymerization on the surface of the particles, or
  • (C) is polymerized in a preceding step as a monomer unit in the polymer I of the particles;
  • step (1) wherein the dispersion resulting from step (1) has a pH of ⁇ 4;
  • redispersible dispersion powder or “redispersible powder” denotes a polymer in powder or particle form, which can be redispersed when a solvent, in particular a polar solvent such as water, is added.
  • the redispersible dispersion powders or the dispersion resulting with the solvent, preferably with water, can be used in building material compositions in order to improve the workability, the flexibility, the adhesive properties and / or the flowability of the building material compositions.
  • the polymer particles of the redispersible dispersion powder are obtained by emulsion polymerization.
  • This is a process of radical polymerization of hydrophobic monomers in an aqueous phase.
  • emulsifiers are added to solubilize the hydrophobic monomers. Suitable emulsifiers are described below and in particular include those having a polyoxyalkylene group.
  • the emulsifiers added in the emulsion polymerization remain adhered to the surface of the formed polymer particles, so that the emulsifier is applied to the surface of the particles by the emulsion polymerization.
  • a water-soluble initiator is added to initiate the polymerization.
  • Typical initiators include thermally decomposing free radical generators, e.g. Peroxides such as Na2S20s or
  • NH4 2S208 or azo compounds photochemical decomposing radical formers, for example azo-bis (isobutyronitrile) (AIBN) or free-radical generators formed by redox reactions, for example the combination of ammonium peroxodisulfate and ascorbic acid.
  • a drying process is carried out to obtain the redispersible dispersion powder. Suitable drying methods are described below.
  • a spray aid is added to the aqueous dispersion. Suitable spray aids for the process according to the invention for the preparation of the redispersible dispersion powders are described below.
  • particles or “polymer particles” in connection with the inventive redispersible dispersion powders refers to polymer particles having a specific particle size D x based on a particle size distribution, wherein x% of the particles have a diameter which is smaller than the D x value.
  • the Dso particle size is the median particle size distribution.
  • the particle size distribution can be measured, for example, by means of dynamic light scattering ISO 22412: 2008.
  • the particle size distribution can be given as volume distribution, surface distribution or number distribution.
  • the D x value refers to the number distribution, where x% of the total number of particles has a smaller diameter.
  • a D 5 o value of the particles in the dispersion resulting from step (1) of 50 to 1000 nm is preferred.
  • the D 50 value of the particles of the redispersible dispersion powder is larger, and it has a D 50 value of 10 to 300 ⁇ preferred for the particles of the redispersible dispersion powder.
  • the particle size measurement of the dispersion powders is based on optically dynamic, digital image processing. A dispersed stream of particles passes two LED strobe light sources, the shadow projections of the particles being detected by two digital cameras. The dry measurement is carried out with the device Camsizer XT from Retsch GmbH using a dispersing pressure of 50 kPa.
  • the particles of the redispersible dispersion powder according to the invention comprise at least one polymer I which contains monomer units which are composed of at least one ethylenically unsaturated monomer.
  • the term "wherein the polymer I contains monomeric units composed of at least one ethylenically unsaturated monomer” refers to a polymer I which is based on at least one ethylenically unsaturated monomer
  • the ethylenically unsaturated monomer according to the present invention is a compound having the following structural formula:
  • R 1 , R 2 , R 3 and R 4 independently of one another are selected from the group consisting of -H, - (C 1 -C 6 ) -alkyl, -O (C 1 -C 6 ) -alkyl, -COOR 5 , - ( C 6) AlkylCOOR 5, -OC (0) (Ci-C6) alkyl, - (C 2 -C 6) alkenyl, and - (C6-Cio) aryl; and
  • R 5 is - (Ci-Cg) alkyl.
  • C x -C y denotes the possible number of carbon atoms in each group
  • (C 1 -C 9) alkyl denotes a linear aliphatic carbon chain containing from 1 to 9 carbon atoms or a branched aliphatic carbon chain containing 4 to 9 carbon atoms.
  • (C 1 -C 6) alkyl denotes a linear aliphatic carbon chain containing from 1 to 6 carbon atoms or a branched aliphatic carbon chain containing from 4 to 6 carbon atoms
  • non-limiting examples (Ci-Cg ) Alkyl groups or (Ci-Ce) alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2 Methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 Ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbuty
  • the (C 1 -C 6) alkyl group may be optionally substituted with one or more substituents independently selected from the group consisting of -F, -Cl, -OH and -CF 3.
  • the term "(C 2 -C 6) alkenyl” denotes a linear or branched alkyl group having 2, 3, 4, 5 or 6 carbon atoms and having one, two or three carbon-carbon double bonds.
  • Non-limiting exemplary (C 2 -C 6) alkenyl groups include vinyl (ethenyl), 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, and 1-hexenyl -C) alkenyl group may optionally be substituted with one or more substituents independently selected from the group consisting of -F, -Cl, -OH and -CF3.
  • (C 6 -C 10) aryl refers to mono- or bicyclic aromatic compounds having 6 or 10 carbon atoms, non-limiting exemplified (C 6 -C 10) aryl groups include phenyl and naphthyl
  • the (C 6 -C 10) aryl group may optionally be substituted with one or more substituents independently selected from the group consisting of -F, -Cl, -OH and -CF 3 , - (Ci-C 6 ) alkyl or -0 (dC 6 ) alkyl substituted.
  • auxiliary monomers may optionally continue to be used in minor amounts, for example in less than 10 wt .-%, preferably less than 8 wt .-%, more preferably less than 6 wt .-%, auxiliary monomers.
  • Examples of these further monomers are ethylenically unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid, aconitic acid, mesaconic acid, crotonic acid, citraconic acid, acryloyloxypropionic acid, methacryloxypropionic acid, vinylacetic acid, monomethylitaconate, monomethyl fumarate, monobutyl fumarate, acrylic acid anhydride, hydride, methacrylic anhydride, maleic anhydride, or itaconic anhydride, acrylamidoglycolic acid and methacrylamidoglycolic acid, acrylamide, methacrylamide, and isopropylacrylamide, substituted (meth) acrylamides, such as N, N-dimethylamino (meth) acrylate; 3-dimethylamino-2,2-dimethylpropyl-1- (meth) acrylate, N, N
  • auxiliary monomers are suitable: ethylenically unsaturated, hydroxyalkyl-functional comonomers, such as methacrylic acid and acrylic acid hydroxy (Ci-C5) -alkylester t as Hydroxyethyl, hydroxypropyl and 4-hydroxybutyl acrylate, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylates, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, and also N-vinylpyrrolidone and vinylimidazole.
  • Particularly preferred are acrylic acid, methacrylic acid, acrylamide, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
  • auxiliary monomers are phosphorus-containing monomers z.
  • vinylphosphonic acid and allylphosphonic acid are also suitable.
  • diesters of phosphonic acid and phosphoric acid which are simply acrylate with a hydroxyalkyl (meth) and additionally simply with a different alcohol, for. As an alkanol, esterified.
  • Suitable hydroxyalkyl (meth) acrylates for these esters are those mentioned below as separate monomers, in particular 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • Corresponding dihydrogenphosphate termonomers include phosphoalkyl (meth) acrylates, such as 2-phosphoethyl (meth) acrylate, 2-phosphopropyl (meth) acrylate, 3-phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate and 3-phospho- 2-hydroxypropyl (meth) acrylate.
  • vinylsulfonic acid allylsulfonic acid, sulfoethyl acrylate, sulfoethyl (meth) acrylate, sulfopropyl acrylate, sulfopropyl (meth) acrylate, 2-hydroxy-3-acryloxypropyl-isulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acids and 2-acrylamido. 2-methyl propane sulfonic acid.
  • Suitable styrenesulfonic acids and derivatives thereof are styrene-4-sulfonic acid and styrene-3-sulfonic acid and the alkaline earth or alkali metal salts thereof, for.
  • sodium styrene-3-sulfonate and sodium styrene-4-sulfonate poly (allyl glycidyl ether) and mixtures thereof, in the form of various products called Bisomer ® Laporte Performance Chemicals, UK. This includes z.
  • Bisomer® MPEG 350 MA a methoxypolyethyl-glycol monomethacrylate.
  • the functional groups of the monomers contribute to the mediation of the colloidal stabilization of the composition, in particular even if the entire formulation also contains fillers, such as calcium carbonate.
  • the crosslinking takes place either by reaction with one another or by addition of a further crosslinking agent.
  • the crosslinking takes place only after the actual film formation.
  • the polymer I contains monomer units selected from at least one ethylenically unsaturated monomer selected from the group consisting of ethylene, propylene, butadiene, styrene, vinyl acetate, vinyl chloride, vinyl ethers, vinyl esters, acrylic acid esters, methacrylic acid esters, and mixtures of previously mentioned monomers are constructed.
  • the polymer I is selected from the group consisting of
  • the polymer I is a styrene-2-ethylhexyl acrylate copolymer, a styrene-n-butyl acrylate copolymer or a styrene-butadiene copolymer.
  • the spray aid used is a polyacid II which comprises monomer units which are composed of at least one ethylenically unsaturated monomer containing a sulfonic acid group.
  • the term "polyacid II, which contains monomer units which are made up of at least one ethylenically unsaturated monomer containing a sulfonic acid group or a salt of this group” refers to a polyacid II which At least one ethylenically unsaturated monomer is derived, wherein the ethylenically unsaturated monomer contains a sulfonic acid group
  • the ethylenically unsaturated double bonds are converted into the polymer chain
  • the sulfonic acid groups are not involved in the polymerization, but are in the side chain of the ethylenically unsatur
  • the "ethylenically unsaturated monomer containing a sulfonic acid group” is preferably a compound having the following structural formula: wherein R 1b is selected from the group consisting of -SO 3 H or a salt thereof, - (C 1 -C 6 ) alkyl, -O (C 1 -C 6 ) alkyl, -COOR 6 , -CONHR 6 , - (C 1 -C 6 ) alkylCOOR 5 , (C 1 -C 6 ) alkylCONHR 5 , -OC (O) (C 1 -C 6 ) alkyl, -NHC (O) (C 1 -C 6) alkyl, - (C 2 -C 6) alkenyl, and - ( C6-Cio) aryl, wherein at least one carbon atom of the groups - (Ci-C 6 ) alkyl, -0 (Ci-C 6 ) alkyl, -COOR
  • R 2 , R 3 and R 4 are independently selected from the group consisting of -H, - (C 1 -C 6 ) alkyl, -O (C 1 -C 6 ) alkyl, -COOR 5 , - (C 1 -C 6 ) alkylCOOR 5 , -OC (O) (C 1 -C 6 ) alkyl, - (C 2 -C 6 ) alkenyl, and - (C 6 -C 10) aryl;
  • R 5 is -H or - (Ci-Cg) alkyl
  • R 6 is - (C 1 -C 9 ) alkyl.
  • R 1b is selected from the group consisting of -SO 3 H or a salt thereof, - (C 1 -C 6 ) alkyl, -O (C 1 -C 6 ) alkyl, -COOR 6 , - (C 1 -C 6 ) Alkyl COOR 5 , -OC (0) (Ci-C 6 ) alkyl, - (C 2 -C 6 ) alkenyl, and - (C 6 -Cio) aryl selected, wherein at least one carbon atom of the groups - (Ci-C 6 ) alkyl, -O (Ci-C 6 ) alkyl, -COOR 6 , - (Ci-C 6 ) alkyl COOR 5 , -OC (0) (Ci-C 6 ) alkyl, - (C 2 -C 6 ) Alkenyl, and - (C 6 -C 10) aryl is substituted with at least one -
  • R 2 , R 3 and R 4 are independently selected from the group consisting of -H, - (C 1 -C 6 ) alkyl, -O (C 1 -C 6 ) alkyl, -COOR 5 , - (C 1 -C 6 ) alkylCOOR 5 , -OC (O) (C 1 -C 6 ) alkyl, - (C 2 -C 6 ) alkenyl, and - (C 6 -C 10) aryl;
  • R 5 is -H or - (Ci-Cg) alkyl
  • R 6 is - (C 1 -C 9 ) alkyl.
  • R 1b is selected from the group consisting of -SO 3 H or a salt thereof, - (C 1 -C 6 ) alkyl, -O (C 1 -C 6 ) alkyl, -OC (O) (C 1 -C 6 ) alkyl , - (C 2 -C 6 ) alkenyl, and - (C 6 -Cio) aryl selected, where at least one carbon atom of the groups - (Ci-Ce) alkyl, -0 (Ci-C6) alkyl AI, -OC ( 0) is (Ci-C 6 ) alkyl, - (C 2 -C 6 ) alkenyl, and - (C 6 -Cio) aryl substituted with at least one -S0 3 H group or a salt of this group.
  • the polyacid II contains monomer units consisting of at least one ethylenically unsaturated monomer containing at least one sulfonic acid group or a salt thereof, selected from the group consisting of vinylsulfonic acid, 2-hydroxy-3- (prop-2-enoyloxy ) propane-1-sulfonic acid, 2-hydroxy-3 - [(meth) acryloyloxy] propane-1-sulfonic acid, 3-allyloxy-2-hydroxypropane-1-sulfonic acid, styrene-3-sulfonic acid, 3- (meth) allyloxy benzene-1-sulphonic acid, ⁇ -methylstyrenesulphonic acid, ⁇ -ethylstyrenesulphonic acid, allyloxybenzenesulphonic acid, (meth) allyloxybenzenesulphonic acid, maleic acid bis (3-sulphopropyl) ester, maleic acid bis (2-sulphoethyl) este
  • the polyacid II monomer units which are composed of the ethylenically unsaturated monomers acrylic acid, methacrylic acid and 2-methyl-2-propene-1-sulfonic acid or the corresponding salts.
  • the polyacid II monomer units which are composed of the ethylenically unsaturated monomers acrylic acid, methacrylic acid and 2-methyl-2-propene-1-sulfonic acid or the corresponding salts, wherein the weight fraction of the monomers of the Acrylic acid 10 to 40 wt .-%, the methacrylic acid 10 to 40 wt .-% and the 2-methyl-2-propene-1-sulfonic acid 10 to 40 wt .-%, based on the total weight of the monomers making up the Polymer II is constructed.
  • the polyacid II monomer units which are composed of the ethylenically unsaturated monomers acrylic acid and 2-methyl-2-propene-1-sulfonic acid or the corresponding salts, wherein the weight fraction of the monomers the acrylic acid is from 20 to 80% by weight and the 2-methyl-2-propene-1-sulfonic acid is from 20 to 80% by weight, based on the total weight of the monomers constituting the polymer II.
  • the polyacid II monomer units which are composed of the ethylenically unsaturated monomers methacrylic acid and 2-methyl-2-propene-1-sulfonic acid or the corresponding salts, wherein the weight fraction of the monomers of methacrylic acid 20 to 80 wt .-% and the 2-methyl-2-propene-1-sulfonic acid 20 to 80 wt .-%, based on the total weight of the monomers of which the polymer II is constructed.
  • the polyacid II contains monomer units which are composed of at least one allylic monomer containing at least one sulfonic acid group or a salt of this group.
  • an allylic monomer containing at least one sulfonic acid group means a monomer containing a 2-propenyl group and at least one sulfonic acid group or a salt thereof.
  • 2-propenyl is to be understood as a monounsaturated C3 group which may be bound to the monomer via an oxygen atom or is directly linked to the sulfonic acid group.
  • the 2-propenyl group is linked directly to the sulfonic acid group.
  • the 2-propenyl group can carry further substituents, preferably a methyl substituent, or be unsubstituted. Due to autoinhibition of the allylic monomer units during free-radical polymerization, cleavage of partial chains can lead to lower molecular weights of the allylic monomer units and thus of the resulting polymers (see "George Odian, Principles of Polymerization, 4th Edition, Wiley-Interscience, 2004") This effect is surprisingly advantageous for the present invention.
  • the polyacid II contains monomer units which comprise at least one allylic monomer containing at least one sulfonic acid group or a salt thereof, selected from the group consisting of 3-allyloxy-2-hydroxypropane-1-sulfonic acid , 3- (Meth) allyloxybenzene-1-sulfonic acid, allyloxybenzenesulfonic acid, (meth) allyloxybenzenesulfonic acid, 2-propene-1-sulfonic acid, 2-methyl-2-propene-1-sulfonic acid and salts of the aforementioned acids and mixtures of the aforementioned monomers , and optionally at least one further ethylenically unsaturated monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid and salts of the aforementioned acids and mixtures of the abovementioned monomers.
  • monomer units which comprise at least one allylic monomer containing at least one sulfonic acid group or
  • the polymer I and the polyacid II can be present independently of one another as a monopolymer (homopolymer) or as a copolymer.
  • the copolymers include random copolymers, gradient copolymers, alternating copolymers, block copolymers and graft copolymers. It is preferred that the copolymers be present as linear random copolymers or as linear block copolymers.
  • the polymer I has a weight average molecular weight of less than 2,500,000 g / mol or less than 1,500,000 g / mol, more preferably from 50,000 to 1,500,000 g / mol.
  • the weight average molecular weight may be determined by gel permeation chromatography, e.g. in THF.
  • the liquid polymer dispersion is dissolved in a large excess of tetrahydrofuran (THF), for example with a polymer concentration of 2 milligrams of polymer per milliliter of THF, and the insoluble fraction separated with a membrane filter of 200 nm mesh size.
  • THF tetrahydrofuran
  • the polyacid II has a weight average molecular weight of less than 250,000 g / mol or less than 150,000 g / mol, more preferably from 1,000 to 50,000 g / mol.
  • the average molecular weight can be determined as weight average by gel permeation chromatography as described in the examples.
  • the polymerization can be carried out by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or precipitation polymerization.
  • a suitable free radical, anionic and / or cationic initiator may be used. Suitable initiators are known to the person skilled in the art.
  • the emulsion polymerization using a radical initiator as stated above is preferred.
  • the solution polymerization using a radical initiator as mentioned above is preferable.
  • a dispersion is obtained by mixing (i) at least one aqueous dispersion comprising particles comprising at least one polymer I and (ii) a polyacid II, characterized the dispersion has a pH of ⁇ 4.
  • a pH of ⁇ 3 is particularly preferred.
  • the pH value can be measured with a pH meter (Ahlborn ALMEMO 2590-9, pH combination electrode: Schott 6381), preferably in accordance with DIN ISO 976 (December 2016).
  • a pH meter Alborn ALMEMO 2590-9, pH combination electrode: Schott 6381
  • the polyacid II not only acts as a spraying aid, but the formed protective casing probably also has a positive influence on the redispersibility of the polymer particles obtainable by the process according to the invention.
  • the pH value is strongly influenced by the pH of the polyacid II and can be influenced by the degree of neutralization of the polyacid.
  • the polyacid II is used as a solution, by adjusting the pH of the solution containing the polyacid II, for example, by adding an acid or base to the solution, it is possible to predict the pH of the dispersion resulting from step (1).
  • the polyacid II can be used in the process of the invention as an aqueous solution or as a solid. Preference is given to using an aqueous solution which already has a pH of ⁇ 4, preferably ⁇ 3, particularly preferably in the range from 1 to 3.
  • an aqueous dispersion having a pH of ⁇ 4, preferably ⁇ 3, particularly preferably in the range from 1 to 3, is then obtained in process step (1).
  • concentrations of the aqueous dispersion containing the particles and the amount of the polyacid II or, if appropriate, the concentration of the aqueous solution containing the polyacid II are preferably selected so that the following ratios of polyacid II based on the weight of the particles or of the Combination of particles and polyacid II based on the total weight of the dispersion can be met.
  • the dispersion resulting from step (1) contains the combination of
  • the dispersion resulting from step (1) contains the combination
  • the amount of solids (without water) based on the total weight of the dispersion refer in each case to the amount of solids (without water) based on the total weight of the dispersion.
  • the amount of the polyacid II relative to the particles (each as a solid) can be varied over a wide range.
  • the polyacid II is preferably in an amount of 2 to 50 wt .-%, more preferably 5 to 40 wt .-%, more preferably 5 to 15 wt .-%, based on the weight of the particles containing at least one polymer I. used.
  • step (2) of the process according to the invention the dispersion resulting from step (1) is dried at the above-indicated pH to obtain the redispersible dispersion powder.
  • the drying can be carried out by roller drying, spray drying, drying in the fluidized bed process, by substance drying at elevated temperature or other conventional drying methods.
  • the preferred range of the drying temperature is between 50 ° C and 230 ° C.
  • a freeze-drying can take place.
  • the process according to the invention comprises, as step (2), the spray-drying of the dispersion resulting from step (1) in order to obtain the redispersible dispersion powder.
  • Preference is given to an inlet temperature of the dry air in the range of 100 ° C to 250 ° C, preferably 130 ° C to 220 ° C and a starting temperature in the range of 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C.
  • Particularly preferred is an inlet temperature in the range of 130 to 150 ° C and an outlet temperature of 60 to 85 ° C.
  • a spray drier from GEA Niro of the Mobile Minor type MM-I can be used.
  • the drying is preferably dried with nitrogen, which is blown in co-current with the drying material from top to bottom. Drying is preferably carried out with 60 to 100 kg / h, more preferably 80 kg / h of drying gas.
  • the powder discharged from the drying tower, with the drying gas, can be separated from the drying gas by means of a cyclone.
  • the method according to the invention further comprises the step
  • Anti-blocking agents reduce the agglomeration of the polymer particles in the redispersible dispersion powder.
  • Non-limiting examples of antiblocking agents are bentonite, quartz sand, quartz flour, kieselguhr, silica, colloidal silica gel, microsilka, fumed silica, or precipitated silica, which may optionally be hydrophobized, clay, magnesium hydrosilicates, talc (magnesium silicate hydrate), calcium hydrosilicates, kaolin (aluminum silicate hydrate), Mica,
  • antiblocking agents are silica, talc, calcium carbonate, kaolin and mixtures thereof.
  • the proportion of the antiblocking agent is preferably between 4 and 20% by weight, based on the total weight of all constituents of the redispersible polymer powder.
  • the antiblocking agent is talc, calcium carbonate and / or silica in a proportion of between 4 to 20 wt .-% based on the total weight of all components of the redispersible polymer powder.
  • one of the antiblocking agents described above may be added during drying. This does not necessarily have to be the same antiblocking agent which is added after drying. Preference is given to adding silica, which may optionally be hydrophobized. If the antiblocking agent is added during drying, the proportion is preferably between 0.1-4.0% by weight, more preferably between 0.5-2.0% by weight, based on the total weight of all constituents of the redispersible polymer powder.
  • an additive which acts as an emulsifier. It is believed that the emulsifier enhances the formation of the protective coating of the polyacid II around the polymer particles.
  • an additive is used in the process according to the invention, which acts as an emulsifier.
  • the additive is particularly preferably used in step (1) of the process. Additives having a polyoxyalkylene group have proved to be particularly advantageous. In a further preferred embodiment of the process according to the invention, therefore, in step (1) an additive comprising a polyoxyalkylene group, preferably a polyoxyethylene group, the degree of ethoxylation being from 6 to 50, is mixed in with the additive
  • (A) is admixed as a further component of the mixture from step (1), or
  • Particles is applied, or
  • (c) is polymerized in a preceding step as a monomer unit in the polymer I of the particles. It is also possible according to the invention that the options (a), (b) and (c) are used in combination.
  • Option (a) is to be understood as meaning that the additive is admixed as a further component of step (1), wherein the additive may be added as an aqueous solution or as a solid.
  • Option (b) is to be understood as meaning that the additive is already present in the emulsion polymerization when the polymer particles containing the polymer I are prepared. As a result, the additive is applied to the surface of the polymer particles, but no covalent bonds are formed, but hydrogen bonds are formed between the polymer chain and the additive.
  • Option (c) is to be understood as meaning that the additive is introduced via the side chain of a monomer which is present in the preparation of polymer I, so that the polymer chain obtained not only has the monomer units characteristic of polymer I, which are more detailed above but also other monomer units resulting from an ethylenically unsaturated monomer containing a polyoxyalkylene group in the side chain.
  • Such monomers are also referred to as polyoxyalkylenated, ethylenically unsaturated monomers according to the invention.
  • the polyoxyalkylene group may be a polyoxy (C 1 -C 4) alkylene group, preferably a polyoxyethylene group.
  • the polyoxyalkylene group of the additive is preferably a polyoxyethylene group wherein the degree of ethoxylation is 6 to 50. It is particularly preferred that the degree of ethoxylation is 10 to 35.
  • the degree of ethoxylation refers to the average number of ethoxy groups (-CH2-CH2-O-) per molecule of additive or per monomer unit in the case of option (c).
  • step (1) an additive comprising a polyoxyethylene group, the degree of ethoxylation being from 6 to 50, being admixed, wherein the additive
  • (A) is admixed as a further component of the mixture from step (1), and / or
  • (B) is applied in a preceding step by emulsion polymerization on the surface of the particles.
  • step (1) an additive comprising a polyoxyethylene group, the degree of ethoxylation being from 6 to 50, being admixed, wherein the additive
  • step (1) is added to the mixture of step (1) as a further component.
  • step (1) an additive containing a polyoxyethylene group wherein the degree of ethoxylation is from 6 to 50 is admixed, wherein the additive
  • step (1) an additive comprising a polyoxyethylene group, wherein the degree of ethoxylation is 6 to 50, is admixed, the additive
  • (c) is polymerized in a preceding step as a monomer unit in the polymer I of the particles.
  • the degree of ethoxylation of the polyoxyethylene group of the additive is 10 to 35.
  • the additives used according to option (a) or (b) are preferably polyoxyalkylenated (C 6 -C 22) alcohols, (C 6 -C 30) -carboxylic acids, (C 6 -C 30) -alkylamines, sorbitan esters, triglycerides or alkylphenols, wherein the polyoxyalkylene group is preferably one of the above-mentioned polyoxyalkylene groups, especially a polyoxyethylene group.
  • (C 6 -C 22) alcohol denotes a linear aliphatic carbon chain containing from 6 to 22 carbon atoms or a branched aliphatic carbon chain containing from 4 to 22 carbon atoms, the carbon chain being substituted by at least one hydroxy group
  • Exemplary compounds include cis-9-hexadecen-1-ol, trans-9-octadecene-1-ol, cis-9-octadecene-1-ol, 1-decanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, iso tridecanol, 2-propyl-4-methylhexanol, 2-propyl-5-methylhexanol, 2-iso-propyl-4-methylhexanol, 2-iso-propyl-5-methylhexanol, 2-propyl-4,4-dimethylhexanol, 2 Ethyl 2-methylheptanol and
  • Non-limiting example compounds of (C6-C30) carboxylic acids include capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, stearic and cerotic acids.
  • Sorbitan esters are cyclic sorbitol esters of (C6-C3o) carboxylic acids.
  • the term "triglyceride” refers to the triesters of glycerol with (C 6 -C 30) carboxylic acids, wherein the (C 6 -C 30) carboxylic acids can also be exchanged by transesterification with a polyalkylene oxide
  • the triglycerides may be of vegetable or animal origin Compounds include pork fat, butter oil, linseed oil, olive oil, palm oil, soybean oil and coconut oil.
  • alkylphenol refers to an ortho, meta or para substituted alkyl substituted phenol.
  • alkyl in the context of alkylphenols refers to a linear or branched aliphatic saturated or unsaturated carbon group which, unless otherwise stated, contains from 1 to 36 carbon atoms.
  • Non-limiting exemplified (C 1 -C 36) alkyl groups in connection with alkylphenols include n-heptyl, n-octyl, 2-ethylhexyl, iso-octyl, nonyl, iso-nonyl, decyl, iso-decyl, cis-6-hexadecene, 2-hexylethyl, and 2-propylheptyl.
  • the additive containing a polyoxyalkylene group in options (a) and (b) is selected from the group consisting of (C6-C22) -alcohol ethoxylates, (C6-C22) -alcohol ether sulfonates and (C6-C22) Alcohol ether sulfates, and is polymerized in option (c) as a polyoxyethylenated ethylenically unsaturated monomer.
  • (C6-C22) -alcohol ether sulfates also called (C6-C22) -alcohol polyglycol ether sulfates (or (C6-C22) -alcohol ether sulfonates) are the sulfates (or sulfonates) of the adducts of polyethylene glycol to a (C6-C22 )
  • the additive containing a polyoxyalkylene group in options (a) and (b) is a (C6-C22) alcohol ethoxylate and / or a (C6-C22) alcohol ether sulfonate or sulfate.
  • the additive containing a polyoxyalkylene group in options (a) and (b) is a C 12 -alcohol ether sulfonate or sulfate (dodecyl ether sulfate).
  • the additives used according to option (a) or (b) are preferably in an amount of 0.2-10% by weight, more preferably in an amount of 0.2-5% by weight, more preferably in an amount of 0.5-5 wt .-%, based on the total weight of the dispersion used.
  • suitable monomers are preferably an amount of 0.2-10% by weight, more preferably in an amount of 0.2-5% by weight, particularly preferably in an amount of 0.5% by weight. 5 wt .-%, based on the total weight of the dispersion, copolymerized in the polymer I of the particles.
  • the preparation of the polymer dispersion is usually carried out in the presence of at least one surface-active compound.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, p. 41 1 to 420.
  • Suitable emulsifiers are also found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.
  • Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers.
  • Emulsifiers whose relative molecular weights are usually below those of protective colloids are preferably used as surface-active substances. In particular, it has proven useful to use exclusively anionic emulsifiers or a combination of at least one anionic emulsifier and at least one nonionic emulsifier.
  • nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C4-C10), ethoxylates of long-chain alcohols (EO degree: 3 to 100, alkyl radical: C) 8 -C 3 6) and polyethylene oxide / polypropylene oxide homo- and copolymers. These may comprise the alkylene oxide units randomly distributed or in copolymerized form in the form of blocks. Well suited z. B. EO / PO block copolymers.
  • Ethoxylates of long-chain alkanols (alkyl radical Cr C30, average degree of ethoxylation 5 to 100) and, with particular preference, those with a linear C 12 -C 20 -alkyl radical and an average degree of ethoxylation of from 10 to 50 and also ethoxylated monoalkylphenols.
  • Suitable anionic emulsifiers are for example alkali metal and ammonium salts of Al kylsulfaten (alkyl radical: C8-C22), ethoxylated sulfuric acid monoesters of alkanols (EO degree: from 2 to 50, alkyl radical: Ci2-Ci8) and ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C4-C9), of alkylsulfonic acids (alkyl radical: C12-C18) and of alkylarylsulfonic acids (alkyl radical: Cg-C-is).
  • emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208.
  • anionic emulsifiers are bis (phenylsulfonic acid) ethers or their alkali metal or ammonium salts which carry a C 4 -C 2 -alkyl group on one or both aromatic rings. These compounds are well known, for. From US4,269,749 A, and commercially available, for example as Dowfax® 2A1 (Dow Chemical Company).
  • Suitable cationic emulsifiers are preferably quaternary ammonium halides, e.g. Trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of N-C6-C20-alkylpyridines, -morpholines or -imidazoles, e.g. B. N-Laurylpyridinium chloride.
  • quaternary ammonium halides e.g. Trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of N-C6-C20-alkylpyridines, -morpholines or -imidazoles, e.g. B. N-Laurylpyridinium chloride.
  • the present invention relates to a redispersible dispersion powder obtainable by the process according to the invention.
  • the redispersible dispersion powder can be redispersed particularly well, which is due to the structural properties which result from the production process according to the invention.
  • the polymer particles are influenced by the polyacid II with respect to the redispersibility, which can be explained by the fact that the polyacid II by hydrogen bonds, which form particularly well at the acidic pH of the dispersion used in the process, a protective cover to the Forms polymer particles.
  • the redispersible dispersion powder preferably also contains an antiblocking agent. Suitable antiblocking agents are those mentioned above.
  • the redispersible dispersion powder may contain, in addition to the antiblocking agent, other additives, e.g. Flame retardants, antioxidants, light stabilizers, biocides, fibrous and powdery fillers or reinforcing agents or antistatic agents, defoamers, thickeners, and other additives, or mixtures thereof. These can either be added after drying, or they can be added before drying, ie in step (1). Only the antiblocking agent is preferred to be added only after drying.
  • a particularly preferred additive is a defoamer, which in turn is preferably added in step (1).
  • the invention further relates to an aqueous dispersion obtainable after step (1) of the process.
  • the acidic pH of the dispersion is advantageous for the spray-drying and the redispersibility of the redispersible dispersion powders which can be prepared in this way.
  • the invention therefore also relates to the use of the aqueous dispersion according to the invention for producing a redispersible dispersion powder.
  • the invention relates to a building material composition containing
  • the building material composition has improved properties in terms of processability, flexibility, adhesion, ductility, abrasion resistance, water-tightness, density, flexural and cohesive strength and / or long-term stability.
  • the building material composition can be used as a coating of surfaces, e.g. To repair unevenness or to make the surface more resistant to corrosion by environmental influences, for example by CO2, SO2, C or salts.
  • the crack-bridging properties can be improved.
  • the invention also relates to the use of the inventive redispersible dispersion powder in a building material composition. It is particularly advantageous that the building material composition can be used as dry mixtures, because the redispersible dispersion powder according to the invention is particularly readily redispersible.
  • redispersible dispersion powder according to the invention for the following building material compositions is advantageous or the following building material compositions according to the invention are preferred:
  • building material compositions are also called base material-modified building material compositions.
  • the building material composition may contain a mineral binder.
  • Mineral binders such as lime, gypsum, cement or mixtures thereof are known in the art. They are used, for example, for the production of mortars and concretes used. Cements in accordance with DIN EN 197-1 (November 201 1) or comparable standards may be considered as cement, for example white cement or gray cement, such as Portland cement, may be used as the cement.
  • cement also includes calcium aluminate cements, calcium sulfo-aluminate cements (CSA cements) and mixtures thereof.
  • Calcium aluminate cements include minerals of the formula CaO x Al 2 O 3. They can be obtained, for example, by melting calcium oxide (CaO) or limestone (CaCC) with bauxite or aluminate. Calcium aluminate cements comprise about 20 to 40 wt .-% CaO, up to 5 wt .-% S1O2, about 40 to 80 wt .-% Al2O3 and up to about 20 wt .-% of Fe 2 0. 3 Calcium aluminate cements are defined in the standard DIN EN 14647 (January 2006).
  • Calcium sulfo-aluminate cements can be prepared from tricalcium aluminate (3 CaO x Al 2 O 3), anhydrite (CaSO 4 ), calcium sulfate hemihydrate (CaSO 4 ⁇ 0.5 H 2 O) and / or gypsum (CaSO 4 ⁇ 2 H 2 O). be presented.
  • Mineral binders also include latent hydraulic binders such as microsilica, meta-tocol, aluminosilicates, fly ash, activated clay, pozzolans or mixtures thereof.
  • latent hydraulic binder we only in the presence of a basic activator hydraulically.
  • the alkaline medium for activating the binders usually consists of aqueous solutions of alkali metal carbonates, alkali metal fluorides, alkali metal hydroxides, alkali metal aluminates and / or alkali metal silicates, such as e.g. soluble water glass.
  • additives such as plasticizers, thickeners or other rheology aids, fillers, air entraining agents, defoamers, accelerators, retarders, wetting aids, etc. may be added.
  • the sample preparation for the molecular weight determination was carried out by dissolving copolymer solution in the GPC eluent so that the polymer concentration in the GPC eluent is 0.5% by weight. Thereafter, this solution was filtered through a syringe filter with Polyethersulfonmembran and pore size 0.45 ⁇ . The injection volume of this filtrate was 50-100 ⁇ .
  • the molecular weights of the copolymers were determined relative to the polyacrylic acid standards of PSS Polymer Standards Service GmbH.
  • the molecular weight distribution curves of the polyacrylic acid standards were determined by light scattering.
  • Dispersion 1 Dispersion 1:
  • the dispersion contains a styrene-2-ethylhexyl acrylate copolymer which still contains monomer units resulting from the stabilizing auxiliary monomers hydroxyethyl methacrylate (HEMA) and 2,3-epoxypropyl methacrylate (GMA).
  • HEMA hydroxyethyl methacrylate
  • GMA 2,3-epoxypropyl methacrylate
  • the dispersion has a solids content of 55% by weight.
  • the polymer has a glass transition temperature of -15 ° C and a particle size of about 600 nm.
  • the dispersion further contains 0.5% by weight of (C 16 -C 18) -alkyl ethoxylate having a degree of ethoxylation of 18, 0.3 Wt .-% of a mixture of sodium di-ethyl-hexylsulphosuccinate / isotridecanol ethoxylate with a degree of ethoxylation of 4 and 0.1 wt.% Ci2-i4-Alkyl (EO) 3 oS0 4 Na.
  • Dispersion 2 :
  • the dispersion contains a styrene-2-ethylhexyl acrylate copolymer which also contains monomer units resulting from the stabilizing auxiliary monomer monomer methoxy poly (oxyethylene) methacrylate having a degree of ethoxylation of 17 and of 2,3-epoxypropyl methacrylate (GMA).
  • the dispersion has a solids content of 56.5% by weight.
  • the poly-mer has a glass transition temperature of -13 ° C and a particle size of about 510 nm.
  • the dispersion further contains 0.5 wt.% Polyoxyethylenated Ci2-C 4 alcohol ethoxylates with a degree of ethoxylation of 4, sulfated and 0.3% sodium lauryl sulfate.
  • the dispersion contains a styrene-butadiene copolymer which still contains monomer units resulting from the stabilizing auxiliary monomers hydroxyethyl methacrylate (HEMA) and acrylic acid.
  • the dispersion has a solids content of 51% by weight.
  • the polymer has a glass transition temperature of 0 ° C and a particle size of about 160 nm.
  • the dispersion further contains 1 wt.% Ci2-i 4 -alkyl (EO) 4 S0 4 Na, 0.7 wt.% Isotridecanolethoxylate with a degree of ethoxylation of 4 and 0.5% by weight of isotridecanol ethoxylates having a degree of ethoxylation of 8.
  • Dispersion 4 The dispersion contains, in addition to the styrene-butadiene copolymer from dispersion 3, 3% by weight (based on the solids content of the dispersion) of isotridecanol ethoxylate with a degree of ethoxylation of 25.
  • Spray auxiliaries (SHM) HSM
  • Spray aid 1
  • the resulting product was a clear polymer solution having a solids content of 52.0% by weight, a pH of 1.4, and a molecular weight M w of about 2400 g / mol.
  • Spray Aid 1A was adjusted to a pH of 2.4 with NaOH.
  • Spray Aid 1 B was adjusted to a pH of 2.4 with NaOH.
  • the spray aid 1A was adjusted to a pH of 3.4 with NaOH.
  • Spray Aid 1A was adjusted to pH 4.2 with NaOH.
  • Spray aid 1A was adjusted to a pH of 6.1 with NaOH.
  • Comparative Spray Aid 2A An aliquot of Spray Aid 2 was adjusted to pH 6.0 with NaOH. Comparative Spray Aid 2B:
  • Spray Aid 2A was adjusted to pH 1.4 with H2SO4.
  • the resulting product was a clear polymer solution having a solids content of 50.3 wt%, a pH of 1.4, and a molecular weight M w of about 1400 g / mol.
  • 280 g of water and 195 g of Na-2-acrylamido-2-methylpropanesulfonic acid (AMPS) were introduced into a reaction vessel equipped with reflux condenser, stirrer, thermometer, dropping funnel and nitrogen gassing and heated to 18 ° C. While stirring, 70 g of a 50% sodium hydroxide solution at 18 ° C were added dropwise. 68 g of acrylic acid, 2.8 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (Wako V50) and 4 g of mercaptoethanol were then metered in over a period of 10 minutes with stirring. The reaction solution was stirred at 70 to 80 ° C for 1, 5 hrs and then cooled to room temperature. The resulting product was a clear polymer solution having a solids content of 48.1% by weight, a pH of 0.8 and a molecular weight M w of about 8400 g / mol.
  • AMPS Na-2-acrylamido-2-methylpropanes
  • the spray drying was carried out with a laboratory dryer (Niro Atomizer) from Niro with nitrogen as the drying gas.
  • the aqueous dispersion to be dried in each case with the water-soluble spray aid was sprayed with a solids content of 40-60% over a two-component nozzle.
  • the inlet temperature of the dryer gas was 130 to 140 ° C, the outlet temperature was 60 to 70 ° C.
  • 0.5 to 1% by weight (based on the solids content of the feed solution) of silica and 9% by weight (based on the solids content of the feed solution) of talc Luzenac (Imerys) were used as antiblocking agents.
  • Films were prepared from the spray-assisted dispersion (SHM) composition shown in Table 1 and their redispersion tested.
  • SHM spray-assisted dispersion
  • the liquid dispersion (5 g of solid) in 10-15 ml of water was mixed with the described amount of the respective spraying aid and dried at 60 ° C. overnight.
  • About 0.5 g of the resulting film was taken up at room temperature in 10 mL of distilled water with stirring (200 rpm). Rapid redispersion within a few minutes has shown that these dispersion systems are also extremely spray-dryable and that a redispersible powder (RDP) is obtained.
  • RDP redispersible powder
  • the redispersion was evaluated as follows:
  • Dispersion SHM of the film of the powder i) 1 1 10 wt.% 1 .4 Very good Very good ü) 1 1 7 wt.% 1 .4 Very good Very good
  • the pH of the dispersion is ⁇ 4 and if the spray assistant is a polyacid composed of at least one ethylenically unsaturated monomer containing a sulfonic acid group.
  • a spraying aid which is based on at least one allylic monomer containing at least one sulfonic acid group.
  • Example 1 is a comparative example in which instead of the redispersible dispersion powder, a styrene-acrylate copolymer (Acronal) was used.
  • the pot life is the period of use in which the polymer-modified building material in the prepared state has a viscosity and creaminess suitable for processing, so that it can be applied to the application substrate with a suitable aid (trowel, doctor blade, etc.). If this time is exceeded, the building material can no longer pass smoothly on the application substrate.
  • a pot life of 0.5-2 hours is desirable, whereas faster systems are difficult to process and extremely slow systems (pot life> 3 hours) delay the next steps.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une poudre de dispersion redispersible, la poudre de dispersion redispersible obtenue selon ce procédé, une dispersion aqueuse pouvant être obtenue par l'étape (1) de ce procédé et une composition de matériaux de construction comprenant la poudre de dispersion redispersible et/ou la dispersion aqueuse, l'utilisation de la poudre de dispersion redispersible dans une composition de matériaux de construction et l'utilisation de la dispersion aqueuse pour préparer une poudre de dispersion redispersible.
EP18727837.9A 2017-06-09 2018-06-06 Procédé de préparation d'une dispersion aqueuse et poudre de dispersion redispersible préparée à partir de celle-ci Pending EP3634921A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17175242 2017-06-09
PCT/EP2018/064815 WO2018224519A1 (fr) 2017-06-09 2018-06-06 Procédé de préparation d'une dispersion aqueuse et poudre de dispersion redispersible préparée à partir de celle-ci

Publications (1)

Publication Number Publication Date
EP3634921A1 true EP3634921A1 (fr) 2020-04-15

Family

ID=59257948

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18727837.9A Pending EP3634921A1 (fr) 2017-06-09 2018-06-06 Procédé de préparation d'une dispersion aqueuse et poudre de dispersion redispersible préparée à partir de celle-ci

Country Status (4)

Country Link
US (1) US11685696B2 (fr)
EP (1) EP3634921A1 (fr)
CN (1) CN110831913B (fr)
WO (1) WO2018224519A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116490479A (zh) * 2020-12-02 2023-07-25 巴斯夫欧洲公司 用于防水覆盖物的组合物
CA3212524A1 (fr) 2021-03-23 2022-09-29 Christian Schmidtke Compositions de poudre de polymere dispersibles dans l'eau pour la cimentation dans une formation souterraine, leur fabrication et leur utilisation
EP4347529A1 (fr) 2021-05-27 2024-04-10 Basf Se Composition de dispersion comprenant une pâte de scellement à base de ciment et un mélange d'additifs
WO2023209082A1 (fr) 2022-04-29 2023-11-02 Basf Se Combinaisons d'un polymère organique et de silicate de calcium hydraté pour la production de membranes d'étanchéité minérales
WO2023237717A1 (fr) 2022-06-10 2023-12-14 Basf Se Auxiliaire de séchage par atomisation pour une poudre de dispersion redispersible
WO2023237718A1 (fr) 2022-06-10 2023-12-14 Basf Se Peinture en poudre comprenant une poudre de dispersion redispersible
CN116947398B (zh) * 2023-09-14 2023-11-24 成都源盟石油科技有限公司 一种树脂水泥浆体及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269749A (en) 1979-04-30 1981-05-26 The Dow Chemical Company Method of imparting salt and/or mechanical stability to aqueous polymer microsuspensions
US4733005A (en) 1986-04-21 1988-03-22 The Dow Chemical Company Phosphinyl-containing ethylenically unsaturated compounds
DE4320220A1 (de) 1993-06-18 1994-12-22 Basf Ag Verwendung von Polymerisaten I, die spezielle monoethylenisch ungesättigte Sulfonsäuren einpolymerisiert enthalten, als Hilfsmittel bei der Sprühtrocknung wäßriger Dispersionen von Polymerisaten II
FR2740357B1 (fr) 1995-10-25 1997-11-28 Rhone Poulenc Chimie Granules redispersables dans l'eau comprenant une matiere active sous forme liquide et un tensio-actif non ionique du type alcoxyles
FR2740462B1 (fr) 1995-10-25 1997-12-19 Rhone Poulenc Chimie Composition pulverulente redispersable dans l'eau de polymeres filmogenes prepares a partir de monomeres a insaturation ethylenique
DE19601699A1 (de) 1996-01-18 1997-07-24 Wacker Chemie Gmbh Redispergierbare Polymerisatpulver und daraus erhältliche wäßrige Polymerisat-Dispersionen
DE19718289A1 (de) * 1997-04-30 1998-11-05 Wacker Chemie Gmbh Verfahren zur Herstellung von wässrigen Polymerdispersionen
DE19750618A1 (de) 1997-11-14 1999-05-20 Basf Ag Pigmenthaltige Zubereitungen auf der Basis wässriger Polymerisatdispersionen
JP4386831B2 (ja) 2002-05-22 2009-12-16 ビーエーエスエフ コンストラクション ポリマース ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリマー分散剤の製造のための乾燥助剤としての水溶性ポリマーの使用
DE10316079A1 (de) * 2003-04-08 2004-11-11 Wacker Polymer Systems Gmbh & Co. Kg Polyvinylalkohol-stabilisierte Redispersionspulver mit verflüssigenden Eigenschaften
EP1923405A1 (fr) 2006-11-17 2008-05-21 Elotex AG Procede de production de dispersions et leur utilisation
PT3157992T (pt) * 2014-06-18 2019-04-12 Basf Se Copolímeros funcionalizados e sua utilização como aglutinante para revestimentos

Also Published As

Publication number Publication date
CN110831913A (zh) 2020-02-21
WO2018224519A1 (fr) 2018-12-13
US20200207671A1 (en) 2020-07-02
CN110831913B (zh) 2023-02-28
US11685696B2 (en) 2023-06-27

Similar Documents

Publication Publication Date Title
WO2018224519A1 (fr) Procédé de préparation d'une dispersion aqueuse et poudre de dispersion redispersible préparée à partir de celle-ci
EP1507819B1 (fr) Utilisation de polymeres hydrosolubles en tant qu'agents dessechants auxiliaires pour la production de dispersants polymeres
EP1086934B1 (fr) Compositions de ciment comprenant des poudres polymères redispersibles
EP1466937B1 (fr) Poudre redispersable stabilisé par le polyvinylalcohol et characterisé par des propriétés fluidifiantes
EP0821660B1 (fr) Procede de conservation d'un corps moule mineral
WO2000047533A1 (fr) Compositions polymeres en poudre a base de polyethercarboxylates
EP1182179B2 (fr) Utilisation de dispersions de polymères libre d'ammoniac comme additif pour des materiaux de construction à base de liants hydrauliques
DE102006050336A1 (de) Geminitensid enthaltende Dispersionspulverzusammensetzungen
DE10332526A1 (de) Redispersionspulver mit puzzolanischen Komponenten
EP0861867B1 (fr) L'utilisation de copolymères d'acides carboxyliques insaturés et leur hydroxyalcoylesters en tant qu'agent assistant le séchage
EP2955165A1 (fr) Composition de liant inorganique comprenant un copolymère
DE19962566A1 (de) Verfahren zur Herstellung von Vinylester-(Meth)acrylsäureester-Mischpolymeri- saten
WO2019038105A1 (fr) Mousse hybride
EP2847290B1 (fr) Utilisation de copolymères comme tackifiants pour des adhésifs
DE10035588A1 (de) Verfahren zur Herstellung von zweiphasigen Polymerisaten in Form deren wässrigen Polymerdispersionen und in Wasser redispergierbaren Polymerpulver
EP1194391B1 (fr) Utilisation de preparations sans polysulfure comme additif pour materiaux de construction a base d'argile
EP2812291B1 (fr) Dispersion aqueuse
EP1347002B1 (fr) Dispersions de polymères comme additif pour des materiaux de construction
EP3097127A1 (fr) Composition de liant
EP2695866B1 (fr) Additif de rhéologie modifié
EP4157804A1 (fr) Procédé de préparation de poudres polymères redispersibles dans l'eau pour formulations sèches de matériaux de construction
DE10260989A1 (de) Verwendung von wasserlöslichen Polymeren als Trocknungshilfsmittel für die Herstellung von Redispersionspulvern und/oder pulverförmiger, polymerer Dispergiermittel
DE10322786A1 (de) Verfahren zur Herstellung von Polymerpulvern
DE19810053A1 (de) Verfahren zum Neutralisieren von wässrigen Dispersionen von filmbildenden Copolymerisaten und so erhältliche Beschichtungen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200109

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20230104